Piperidine-triazine compounds for use as stabilizers for organic materials

ABSTRACT

Piperidine-triazine compounds of the general formula (I)   &lt;IMAGE&gt; (I)  in which R1 is e.g. hydrogen or methyl, R2 is e.g. C2-C6alkylene, R3 is e.g. a group  &lt;IMAGE&gt;  and  w is e.g. 2 or 3, if w is 2, A is    &lt;IMAGE&gt;  and  if w is 3, A is e.g.    &lt;IMAGE&gt;  can be used as light stabilizers, heat stabilizers and oxidation stabilizers for organic materials, in particular synthetic polymers.

The present invention relates to novel piperidine-triazine compounds, totheir use as light stabilizers, heat stabilizers and oxidationstabilizers for organic materials, in particular synthetic polymers, andto the organic materials thus stabilized.

It is known that synthetic polymers undergo a photo-oxidativedegradation when they are exposed to sunlight or other sources ofultraviolet light in the presence of oxygen.

When they are used in practice, it is therefore necessary to add to themsuitable light stabilizers, such as certain benzophenone orbenzotriazole derivatives, nickel complexes, substituted benzoic acidesters, alkylidenemalonates, cyanoacrylates, aromatic oxamides orsterically hindered amines.

Some triazine derivatives of 2,2,6,6-tetramethyl-4-piperidylamine andtheir use as stabilizers for synthetic polymers have been described inU.S. Pat. No. 4,108,829, 4,288,593, 4,376,836, 4,433,145 and 4,533,688and in European Pat. No. 176,106.

In particular, the present invention relates to novel compounds of thegeneral formula (I) ##STR4## in which R₁ is hydrogen, C₁ -C₈ alkyl, O.,OH, NO, CH₂ CN, C₁ -C₁₈ alkoxy, C₅ -C₁₂ cycloalkoxy, C₃ -C₆ alkenyl, C₇-C₉ phenylalkyl which is unsubstituted or mono-, di- or tri-substitutedon the phenyl by C₁ -C₄ alkyl, C₁ -C₈ acyl or C₂ -C₄ alkyl substitutedin the 2-, 3- or 4-position by OH, R₂ is C₂ -C₁₂ alkylene, R₃ is a groupof the formula (II) ##STR5## with R₁ and R₂ being as defined above, orR₃ is a group --OR₄, --SR₄ or ##STR6## in which R₄ is C₁ -C₁₈ alkyl, C₅-C₁₂ cycloalkyl which is unsubstituted or mono-, di- or tri-substitutedby C₁ -C₄ alkyl, C₃ -C₁₈ alkenyl, phenyl which is unsubstituted ormono-, di- or tri-substituted by C₁ -C₄ alkyl, C₇ -C₉ -phenylalkyl whichis unsubstituted or mono-, di- or tri-substituted on the phenyl by C₁-C₄ alkyl, or a group of the formula (III) ##STR7## where R₇ has any ofthe meanings given for R₁, R₅ and R₆ which can be identical or differentare hydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which is unsubstitutedor mono-, di- or tri-substituted by C₁ -C₄ alkyl, C7-C9phenylalkyl whichis unsubstituted or mono-, di- or tri-substituted on the phenyl by C₁-C₄ alkyl, C₂ -C₄ alkyl substituted in the 2-, 3- or 4- position by OH,by C₁ -C₈ alkoxy or by di-(C₁ -C₄ alkyl)-amino, C₃ -C₁₈ -alkenyl,tetrahydrofurfuryl or a group of the formula (III), or R₅ and R₆,together with the nitrogen atom to which they are linked, form part of a5-membered to 7-membered heterocyclic ring, and w is an integer from 2to 6, and if w is 2, A is one of the groups of the formula (IVa)-(IVd)##STR8## in which R₈ is C₂ -C₁₂ alkylene, cyclohexylene,cyclohexylenedimethylene, methylenedicyclohecxylene, (C₂ -C₆alkylidene)-dicyclohexylene, phenylene, (C₂ -C₆ alkylidene)-iiphenylene,xylylene or C₄ -C₁₂ alkylene interrupted by 1, 2 or 3 oxygen atoms, R₉and R₁₁ which can be identical or different are hydrogen, C₁ -C₁₈ alkyl,C₅ -C₁₂ cycloalkyl which is unsubstituted or mono-, di- ortri-substituted by C₁ -C₄ alkyl, C₇ -C₉ phenylalkyl which isunsubstituted or mono-, di- or tri-substituted on the phenyl by C₁ -C₄alkyl, or a group of the formula (III), R₁₀ is as defined above for R₈or C₄ -C₁₂ alkylene interrupted by 1 or 2 groups N-R₁₅ where R₁₅ has anyof the meanings given for R₉ and R₁₁, or is one of the groups of theformula (Va)-(Vd) ##STR9## where R₁₆ is hydrogen, C₁ -C₁₈ alkyl, C₅ -C₁₂cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C₁-C₄ alkyl, C₂ -C₁₈ alkenyl, phenyl which is unsubstituted or mono-, di-or tri-substituted by C₁ -C₄ alkyl and/or an OH group, C₇ -C₉phenylalkyl which is unsubstituted or mono-, di- or tri-substituted onthe phenyl by C₁ -C₄ alkyl and/or an OH group, R₁₇ is C₁ -C₁₈ alkyl, C₅-C₁₂ cycloalkyl which is unsubstituted or mono-, di- or tri-substitutedby C₁ -C₄ alkyl, C₃ -C₁₈ alkenyl or a group of the formula (III), R₁₈ isC₁ -C₁₈ alkyl or phenyl which is unsubstituted or mono-, di- ortri-substituted by C₁ -C₄ alkyl, m is zero or 1, R₁₂ is hydrogen ormethyl, n is zero, 1, 2, 3 or 4, R₁₃ and R₁₄ which are identical ordifferent are as defined above for R₉ and R₁₁, p and q which can beidentical or different are integers from 2 to 6 and r is zero or 1, and,if w is 3, A is one of the groups of the formula (VIa)-(VIc) ##STR10##in which R₁₉, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ and R₂₈ which can be identical ordifferent are as defined above for R₉ and R₁₁ ; R₂₀ and R₂₁ which can beidentical or different are C₂ -C₁₂ alkylene or C₄ -C₁₂ alkyleneinterrupted by a group N-R₂₉ being defined as above for R₁₅, s and vwhich can be identical or different are integers from 2 to 6, t is zeroor 1 and R₂₇ is C₂ -C₁₂ alkylene, and if w is 4, 5 or 6, A isadditionally a group of the formula (VIII) ##STR11## in which R₃₀ andR₃₃ which can be identical or different are as define above for R₉ andR₁₁ ; R₃₁ and R₃₂ which can be identical or different are C₂ -C₁₂alkylene and x is 1, 2 or 3, and, if w is 4, A is also one of the groupsof the formula (VIIIa)-(VIIIc) ##STR12## in which R₃₄, R₃₇, R₃₈ and R₄₁which can be identical or different are as defined above for R₉ and R₁₁; R₃₅, R₃₆, R₃₉ and R₄₀ which can be identical or different are C₂ -C₁₂alkylene, D₁ is C₂ -C₁₂ alkylene, 2-hydroxytrimethylene, --CH₂ CO--,xylylene or one of the groups of the formula (IXa) or (IXb) ##STR13## inwhich R₄₃ is a direct bond, C₁ -C₁₂ alkylene, cyclohexylene orphenylene, R₄₄ is as defined above for R₈ and R₄₂ is as defined abovefor R₃, and, if w is 6, A is also one of the groups of the formula(Xa)-(Xc) ##STR14## in which R₄₅, R₄₉, R₅₀ and R₅₃ which can beidentical or different are as defined above for R₉ and R₁₁ ; R₄₆, R₄₇,R₄₈, R₅₁ and R₅₂ which can be identical or different are C₂ -C₁₂alkylene and D₂ is as defined above for D₁.

Representative examples of C₁ -C₈ alkyl R₁ and R₇ are methyl, ethyl,propyl, butyl, isobutyl, pentyl, hexyl, heptyl and octyl. C₁ -C₄ alkyl,in particular methyl, is preferred.

Examples of C₁ -C₁₈ alkyl are methyl, ethyl, propyl, isopropyl, butyl,2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl,2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, hexadecyl and octadecyl.

Examples of OH-substituted C₂ -C₄ alkyl are 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl and 4-hydroxybutyl.2-Hydroxyethyl is preferred.

Examples of C₂ -C₄ alkyl substituted by C₁ -C₈ alkoxy, preferably C₁ -C₄alkoxy, in particular methoxy or ethoxy, are 2-methoxyethyl,2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl,3-octoxypropyl and 4-methoxybutyl.

Examples of C₂ -C₄ alkyl substituted by di-(C₁ -C₄ alkyl)-amino,preferably dimethylamino or diethylamino, are 2-dimethylaminoethyl,2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl,3-dibutylaminopropyl and 4-diethylaminobutyl.

Representative examples of C₁ -C₁₈ alkoxy R₁ and R₇ are methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy andoctadecyloxy. C₆ -C₁₂ Alkoxy, in particular heptoxy or octoxy, arepreferred.

Examples of unsubstituted or substituted C₅ -C₁₂ cycloalkyl arecyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl,methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl,t-butylcyclohexyl, cyclooctyl, cyclodecyl and cyclododecyl. Cyclohexylis preferred.

Representative examples of C₅ -C₁₂ cycloalkoxy R₁ and R₇ arecyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy andcyclododecyloxy. Cyclopentoxy and cyclohexoxy are preferred.

Examples of alkenyl having up to 18 carbon atoms are vinyl, allyl,2-methylallyl, hexenyl, decenyl, undecenyl, heptadecenyl and oleyl.Allyl is one of the preferred definitions of R₁ and R₇. In alkenyl R₁,R₄ -R₇ and R₁₇, the carbon atom in the 1-position is preferably asaturated carbon atom.

Examples of substituted phenyl are methylphenyl, dimethylphenyl,trimethylphenyl, t-butylphenyl, di-t-butylphenyl, hydroxyphenyl and3,5-di-t-butyl-4-hydroxyphenyl.

Examples of phenylalkyl which is unsubstituted or substituted on thephenyl are benzyl, methylbenzyl, dimethylbenzyl, t-butylbenzyl,2-phenylethyl and 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl.

Acyl R₁ and R₇ having up to 8 carbon atoms can be an aliphatic oraromatic group. Representative examples are formyl, acetyl, propionyl,butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, acryloyl and crotonyl.C₁ -C₈ alkanoyl, C₃ -C₈ alkenoyl and benzoyl are preferred. Acetyl isparticularly preferred.

Representative examples of R₅ and R₆ which, together with the nitrogenatom to which they are linked, form part of a 5-membered to 7-memberedheterocyclic ring preferably containing a further heteroatom, forexample nitrogen or oxygen, are 1-pyrrolidyl, 1-piperidyl,4-morpholinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl,5,5,7-trimethyl-1-homopiperazinyl and4,5,5,7-tetramethyl-1-homopiperazinyl. 4-Morpholinyl is particularlypreferred.

Examples of alkylene having up to 12 carbon atoms are methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene,decamethylene and dodecamethylene. R₂, R₁₀, R₂₀, R₂₁, R₃₁ and R₃₂ arepreferably C₂ -C₆ alkylene.

Examples of C₄ -C₁₂ alkylene interrupted by 1, 2 or 3 oxygen atoms are3-oxapentane-1,5-diyl, 3,6-dioxaoctane-1,8-diyl and3,6,9-trioxaundecane-1,11-diyl.

Representative examples of C₄ -C₁₂ alkylene R₁₀ interrupted by 1 or 2groups ##STR15## are the groups. in which R₁₅ has any of the meaningsgiven above, preferably hydrogen, methyl or (C₂ -C₄ alkoxy)-carbonyl.

Representative examples of alkylene R₂₀ and R₂₁ interrupted by a group##STR16## are the groups in which R₂₉ has any of the meanings givenabove, preferably hydrogen, methyl or (C₂ -C₄ alkoxy)-carbonyl.

An example of (C₂ -C₆ alkylidene)-dicyclohexylene isisopropylidenedicyclohexylene, and an example of (C₂ -C₆alkylidene)-dephenylene is isopropylidenediphenylene.

R₁ is preferably hydrogen, C₁ -C₄ alkyl, OH, C₆ -C₁₂ alkoxy, C₅ -C₈-cycloalkoxy, allyl, benzyl, acetyl or 2-hydroxyethyl, in particularhydrogen or methyl.

Those compounds of the formula (I) are preferred in which R₂ is C₂ -C₁₀-alkylene, R₃ is a group of the formula (II), a group --OR₄, --SR₄ or##STR17## in which R₄ is C₁ -C₁₂ alkyl, C₅ -C₈ cycloalkyl which isunsubstituted or mono-, di- or tri-substituted by C₁ -C₄ alkyl, C₃ -C₁₂alkenyl, phenyl, benzyl or a group of the formula (III), R₅ and R₆ whichcan be identical or different are hydrogen, C₁ -C₁₈ alkyl, C₅ -C₈cycloalkyl which is unsubstituted or mono-, di- or tri-substituted by C₁-C₄ alkyl, benzyl, C₂ -C₃ alkyl substituted in the 2- or 3-position byOH, by C₁ -C₄ -alkoxy or by di-(C₁ -C₄ alkyl)-amino, allyl, oleyl,tetrahydrofurfuryl or a group of the formula (III), or the groups##STR18## is 1-pyrrolidyl, 1-piperidyl, 4-morpholinyl or1-hexahydroazepinyl, w is an integer from 2 to 6 and, if w is 2, A isone of the groups of formula (IVa)-(IVd) in which R₈ is C₂ -C₁₀alkylene, cyclohexylene, cyclohexylenedimethylene,methylenedicyclohexylene, isopropylidenedicyclohexylene,isopropylidenediphenylene or C₄ -C₁₀ alkylene interrupted by 1, 2 or 3oxygen atoms, R₉ and R₁₁ which can be identical or different arehydrogen, C₁ -C₁₂ alkyl, C₅ -C₈ cycloalkyl which is unsubstituted ormono-, di- or trisubstituted by C₁ -C₄ alkyl, benzyl or a group of theformula (III), R₁₀ is as defined above for R₈ or is C₄ -C₁₂ alkyleneinterrupted by 1 or 2 groups ##STR19## where R₁₅ has any of the meaningsgiven for R₉ and R₁₁, or is one or the groups of the formula (Va)-(Vd)in which R₁₆ is hydrogen, C₁ -C₁₇ alkyl, C₅ -C₈ cycloalkyl which isunsubstituted or mono-, di-or tri-substituted by C₁ -C₄ alkyl, C₂ -C₁₇alkenyl, phenyl which is unsubstituted or mono-, di- or tri-substitutedby C₁ -C₄ alkyl and/or an OH group, C₇ -C₈ phenylalkyl which isunsubstituted or mono-, di- or trisubstituted on the phenyl by C₁ -C₄alkyl and/or an OH group, R₁₇ is C₁ -C₁₈ alkyl, C₅ -C₈ cycloalkyl whichis unsubstituted or mono-, di- or tri-substituted by C₁ -C₄ alkyl, C₃-C₁₈ alkenyl or a group of the formula (III) and R₁₈ is C₁ -C₁₂ alkyl,phenyl or tolyl, m is zero or 1, R₁₂ is hydrogen or methyl, n is zero,1, 2, 3 or 4, R₁₃ and R₁₄ which can be identical or different are asdefined above for R₉ and R₁₁, p and q which can be identical ordifferent are 2 or 3 and r is zero or 1, and, if w is 3, A is one of thegroups of the formula (VIa)-(VIc) in which R₁₉, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆and R₂₈ which can be identical or different are as defined above for R₉and R₁₁ ; R₂₀ and R₂₁ which can be identical or different are C₂ -C₁₀alkylene or C₄ -C₁₂ alkylene which is interrupted by a group ##STR20##with R₂₉ being as defined above for R₁₅, s and v which can be identicalor different are integers from 2 to 6, t is zero or 1 and R₂₇ is C₂ -C₁₀alkylene, and, if w is 4, 5 or 6, A is a group of the formula (VII) inwhich R₃₀ and R₃₃ which can be identical or different are as definedabove for R₉ and R₁₁ ; R₃₁ and R₃₂ which can be identical or differentare C₂ -C₁₀ alkylene and x is 1, 2 or 3, and, if w is 4, A can also beone of the groups of the formula (VIIIa)-(VIIIc) in which R₃₄, R₃₇, R₃₈and R₄₁ which can be identical or different are as defined above for R₉and R₁₁ ; R₃₅, R₃₆, R₃₉ and R₄₀ which can be identical or different areC₂ -C₁₀ alkylene, D₁ is C₂ -C₁₀ alkylene, 2-hydroxytrimethylene, --CH₂CO--, xylylene or one of the groups of the formula (IXa) or (IXb) inwhich R₄₃ is a direct bond or C₁ -C₁₀ alkylene, R₄₄ is as defined abovefor R₈ and R₄₂ is as defined above for R₃ and, if w is 6, A is also oneof the groups of the formula (Xa)-(Xc) in which R₄₅, R₄₉, R₅₀ and R₅₃which can be identical or different are as defined above for R₉ and R₁₁; R₄₆, R₄₇, R₄₈, R₅₁ and R₅₂ which can be identical or different are C₂-C₁₀ alkylene and D₂ is as defined above for D₁.

Those compounds of the formula (1) are particularly preferred in whichR₂ is C₂ -C₈ alkylene, R₃ is a group of the formula (II), a group --OR₄or ##STR21## in which R₄ is C₁ -C₈ alkyl, cyclohexyl which isunsubstituted or mono-, di- or tri-substituted by C₁ -C₄ alkyl, allyl,undecenyl, phenyl, benzyl or a group of the formula (III), R₅ and R₆which can be identical or different are hydrogen, C₁ -C₁₂ alkyl,cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C₁-C₄ alkyl, benzyl, C₂ -C₃ alkyl substituted in the 2- or 3-position byOH, by methoxy, by ethoxy, by dimethylamino or by diethylamino, allyltetrahydrofurfuryl or a group of the formula (III), or the group##STR22## is 4-morpholinyl, w is an integer from 2 to 6 and, if 1 is 2,A is one of the groups of the formula (IVb)-(IVd) in which R₉ and R₁₁which can be identical or different are hydrogen, C₁ -C₈ alkyl,cyclohexyl which is unsubstituted or mono-, di- or trisubstituted by C₁-C₄ alkyl, benzyl or a group of the formula (III), R₁₀ is C₂ -C₈alkylene, cyclohexylenedimethylene, methylenedicyclohexylene, C₄ -C₈alkylene interrupted by 1 or 2 oxygen atoms or C₄ -C₁₂ alkyleneinterrupted by 1 or 2 groups ##STR23## where R₁₅ has any of the meaningsgiven for R₉ and R₁₁, or is one of the groups of the formula (Va)-(Vc)in which R₁₆ is C₁ -C₁₇ alkyl, cyclohexyl which is unsubstituted ormono-, di- or tri-substituted by C₁ -C₄ alkyl, C₂ -C₁₀ alkenyl, phenyl,3,5-di-t-butyl-4-hydroxyphenyl, benzyl or2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl, R₁₇ is C₁ -C₁₈ alkyl,cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C₁-C₄ alkyl, allyl, undecenyl, oleyl or a group of the formula (III), m iszero or 1, R₁₂ is hydrogen or methyl, n is zero, 1, 2 or 3, R₁₃ and R₁₄which can be identical or different are as defined above for R₉ and R₁₁,p and q which can be identical or different are 2 or 3 and r is zero or1, and, if w is 3, A is a group of the formula (VIa) in which R₁₉ andR₂₂ which can be identical or different are as defined above for R₉ andR₁₁ ; R₂₀ and R₂₁ which can be identical or different are C₂ -C₈alkylene and R₂₀ is also C₄ -C₁₂ alkylene interrupted by a group##STR24## with R₂₉ being as defined above for R₁₅, and, if w is 4, 5 or6, A is a group of the formula (VII) in which R₃₀ and R₃₃ which can beidentical or different are as defined above for R₉ and R₁₁ ; R₃₁ and R₃₂which can be identical or different are C₂ -C₈ alkylene and x is 1, 2 or3, and, if w is 4, A is also a group of the formula (VIIIa) in which R₃₄and R₃₇ which can be identical or different are as defined above for R₉and R₁₁ ; R₃₅ and R₃₆ which can be identical or different are C₂ -C₈alkylene and D₁ is C₂ -C₈ alkylene, 2-hydroxytrimethylene, xylylene or agroup of the formula (IXa) or (IXb) in which R₄₃ is a direct bond or C₁-C₈ alkylene and R₄₄ is C.sub. 4 -C₈ alkylene, 3-oxapentane-1,5-diyl,cyclohexylenedimethylene or isopropylidenedicyclohexylene and, if w is6, A is also a group of the formula (Xa) in which R₄₅ and R₄₉ which canbe identical or different are as defined above for R₉ and R₁₁ ; R₄₆, R₄₇and R₄₈ which can be identical or different are C₂ -C₈ alkylene and D₂is as defined above for D₁.

Those compounds of the formula (I) are of special interest in which R₂is C₂ -C₆ alkylene, R₃ is a group of the formula (II) or a group##STR25## in which R₅ and R₆ which can be identical or different are C₁-C₈ alkyl, cyclohexyl, benzyl, C₂ -C₃ alkyl which is substituted in the2- or 3-position by methoxy, by ethoxy, by dimethylamino ordiethylamino, allyl, tetrahydrofurfuryl, 2,2,6,6-tetramethyl-4-piperidylor 1,2,2,6,6-pentamethyl-4-piperidyl, or R₅ is also hydrogen, or thegroup ##STR26## is 4-morpholinyl, and w is 2, 3 or 4, and, if w is 2, Ais one of the groups of the formula (IVb)-(IVd) in which R₉ and R₁₁which can be identical or different are hydrogen, C₁ -C₄ alkyl,cyclohexyl, 2,2,6,6-tetramethyl-4-piperidyl or1,2,2,6,6-pentamethyl-4-piperidyl, R₁₀ is C₂ -C₆ alkylene,cyclohexylenedimethylene, methylenedicyclohexylene or C₄ -C₁₂ alkyleneinterrupted by 1 or 2 groups ##STR27## where R₁₅ is hydrogen, methyl ora group of the formula (Va) or (Vb) in which R₁₆ is C₁ -C₁₇ alkyl,cyclohexyl, phenyl or 2-(3,5-di-t-butyl-4-hydroxyphenyl)-ethyl and R₁₇is C₂ -C₁₈ alkyl, cyclohexyl, t-butylcyclohexyl or1,2,2,6,6-pentamethyl-4-piperidyl and m and n are zero, R₁₃ and R₁₄which can be identical or different are as defined above for R₉ and R₁₁,p and q are 2 or 3 and r is zero or 1, and, if w is 3, A is a group ofthe formula (VIa) in which R₁₉ and R₂₂ which can be identical ordifferent are as defined above for R₉ and R₁₁ ; R₂₀ and R₂₁ which can beidentical or different are C₂ -C₆ -alkylene and R₂₀ is also C₄ -C₆alkylene interrupted by a group ##STR28## with R₂₉ being as definedabove for R₁₅, and, if w is 4, A is a group of the formula (VII) inwhich R₃₀ and R₃₃ which can be identical or different are as definedabove for R₉ and R₁₁ ; R₃₁ and R₃₂ which can be identical or differentare C₂ -C₆ alkylene and x is 1, or A is a group of the formula (VIIIa)in which R₃₄ and R₃₇ which can be identical or different are as definedabove for R₉ and R₁₁ ; R₃₅ and R₃₆ which can be identical or differentare C₂ -C₆ alkylene and D₁ is a group of the formula (IXa) or (IXb) inwhich R₄₃ is C₂ -C₈ alkylene and R₄₄ is C₄ -C₆ alkylene,3-oxapentane-1,5-diyl, cyclohexylenedimethylene orisopropylidenedicyclohexylene.

Those compounds of the formula (I) are of particular interest in whichR₁ is hydrogen or methyl, R₂ is --(CH₂)₂₋₆ -, R₃ is a group of theformula (II) with R₁ and R₂ being as defined above, w is 2, 3 or 4 and,if w is 2, A is one of the groups of the formula (IVb)-(IVd) in which R₉and R₁₁ which can be identical or different are hydrogen, methyl,2,2,6,6-tetramethyl-4-piperidyl or 1,2,2,6,6-pentamethyl-4-piperidyl,R₁₀ is C₂ -C₆ -alkylene, methylenedicyclohexylene, C₄ -C₁₂ alkyleneinterrupted by 1 or 2 groups ##STR29## where R₁₅ is hydrogen, methyl ora group of the formula (Va) or (Vb) in which R₁₆ is C₄ -C₁₇ alkyl andR₁₇ is C₂ -C₁₈ alkyl or t-butylcyclohexyl, m and n are zero, R₁₃ and R₁₄which can be identical or different are as defined above for R₉ and R₁₁,p and q are 2 or 3 and r is zero or 1, and, if w is 3, A is a group ofthe formula (VIa) in which R₁₉ and R₂₂ which can be identical ordifferent are as defined above for R₉ and R₁₁ ; R₂₀ and R₂₁ which can beidentical or different are C₂ -C₆ -alkylene and R₂₀ is also C₄ -C₆alkylene interrupted by a group ##STR30## with R₂₉ being as definedabove for R₁₅, and, if w is 4, A is a group of the formula (VII) inwhich R₃₀ and R₃₃ which can be identical or different are hydrogen ormethyl, R₃₁ and R₃₂ which can be identical or different are C₂ -C₃alkylene and x is 1.

A further preferred embodiment is that in which R₁ is hydrogen ormethyl, R₂ is C₂ -C₆ alkylene, R₃ is a group of the formula (II) with R₁and R₂ being as defined above and w is 2, 3 or 4, and, if w is 2, A ispiperazine-1,4-diyl or a group of the formula (IVb) in which R₉ and R₁₁which can be identical or different are hydrogen, methyl,2,2,6,6-tetramethyl-4-piperidyl, or 1,2,2,6,6-pentamethyl-4-piperidyl,R₁₀ is C₂ -C₆ alkylene, methylenedicyclohexylene or C₄ -C₁₂ alkyleneinterrupted by 1 or 2 groups ##STR31## where R₁₅ is hydrogen, methyl or(C₂ -C₄ alkoxy)-carbonyl, and, if w is 3, A is a group of the formula(VIa) in which R₁₉ and R₂₂ which can be identical or different arehydrogen or methyl, R₂₀ is C₂ -C₆ alkylene or C₄ -C₆ alkyleneinterrupted by a ##STR32## with R₂₉ being as defined above for R₁₅ andR₂₁ is C₂ -C₆ alkylene, and, if w is 4, A is a group of the formula(VII) where R₃₀ and R₃₃ which can be identical or different are hydrogenor methyl, R₃₁ and R₃₂ independently of one another are C₂ -C₃ alkyleneand x is 1.

The compounds of the formula (I) can be prepared analogously to knownprocesses, for example as described in U.S. Pat. No. 4,108,829.

It is preferable first to prepare the compounds of the formula (Ia)##STR33## with R₂, R₃, A and w being as defined above, from which thecorresponding compounds of the formula (I) with R₁ different from H canthen be obtained.

The compounds of the formula (Ia) can be prepared, for example, byreacting, in any order, cyanuric chloride with the compounds of theformula (XIa)-(XIc) ##STR34## utilizing the appropriate molar ratios.

If R₁₀, R₂₀ and R₂₁ are C₄ -C₁₂ -alkylene interrupted by 1 or 2 groups##STR35## or by a groups ##STR36## the compounds of the formula (Ia) arepreferably prepared by reacting the corresponding compounds with R₁₅ andR₂₉ =H with suitable alkylating or acylating reagents.

If A is a group of the formula (VIIIa) or (Xa), the compounds of theformula (Ia) are preferably prepared by reacting a compound of theformula (XIIa) or (XIIb) respectively ##STR37## in which Z is a group ofthe formula (XIII) ##STR38## with the compound of the formula (XIV)

    E-D-E                                                      (XIV)

in which E is, for example, chlorine or bromine and D is as definedabove for D₁ or D₂, or with epichlorohydrin if D₁ and D₂ are2-hydroxytrimethylene.

If R₁ is methyl, the compounds of the formula (I) are preferablyprepared by reacting the corresponding compounds of the formula (Ia)with formaldehyde and formic acid (Eschweiler-Clarke reaction), or withformaldehyde and hydrogen in the presence of a hydrogenation catalyst,for example palladium or platinum.

In these reactions, the non-piperidine ##STR39## amine groups and, underappropriate conditions, also the melamine groups which may be presentcan also be methylated.

The reactions of cyanuric chloride with the compounds of the formula(XIa)-(XIc) are preferably carried out in an aromatic hydrocarbonsolvent, for example toluene, xylene, trimethylbenzene or decalin,operating at a temperature from e.g. -30° to 40° C., preferably from-20° to 20° C., for the substitution of the first Cl, from e.g. 40° to100° C., preferably from 50° to 90° C., for the substitution of thesecond Cl and from e.g. 100° to 200° C., preferably from 120° to 180°C., for the substitution of the third Cl.

The hydraulic acid liberated in the various reactions is neutralizedwith a preferably inorganic base, for example with sodium or potassiumhydroxide or carbonate, in a quantity at least equivalent to the acidliberated.

The compounds of the formula (XIa) can be prepared, for example,according to scheme 1 by reacting a compound of the formula (XV) with 2mols of 2,2,6,6-tetramethyl-4-piperidone to give an enamine-ketimine ofthe formula (XVI) which is then hydrogenated in the presence of ahydrogenation catalyst such as platinum, palladium or nickel. ##STR40##

The reactions according to scheme 1 are preferably carried out in thesame reactor without isolating the intermediate of the formula (XVI),operating without solvent or in the presence of an aliphatic or aromatichydrocarbon solvent having a boiling point e.g. from 60° to 180° C. ,preferably from 80° to 140° C.; the hydrogenation can also be carriedout in the presence of a C₁ -C₄ alcohol.

The compounds of the formula (XIa) can also be prepared, for example,directly by catalytic hydrogenation of a mixture of2,2,6,6-tetramethyl-4-piperidone and a compound of the formula (XV) in amolar ratio of 2/1, without solvent or in a C₁ -C₄ alcohol, preferablyin the presence of an organic or inorganic acid, for example benzoicacid or sulphuric acid, in a quantity from 0.001 to 0.05 mol per mol of2,2,6,6-tetramethyl-4-piperidone.

The other intermediates of the formula (XIb) and (XIc) are commercialproducts which can be prepared by known processes.

As mentioned at the outset, the compounds of the formula (I) are highlyeffective in improving the light stability, heat stability and oxidationstability of organic materials, in particular synthetic polymers andcopolymers.

The invention therefore also relates to a composition comprising anorganic material, which is susceptible to light-induced, thermal oroxidative degradation, and at least one compound of the formula (I).

Examples of organic materials which can be stabilized are:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high-density polyethylene (HDPE), low-densitypolyethylene (LDPE) and linear low-density polyethylene (LLDPE).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, such as, for example, ethylene/propylene, linearlow-density polyethylene (LLDPE) and its mixtures with low-densitypolyethylene (LDPE), propylene/butene-1, ethylene/hexene,ethylene/ethylpentene, ethylene/heptene, ethylene/octene,propylene/isobutylene, ethylene/butene-1, propylene/butadiene,isobutylene/isoprene, ethylene/alkyl acrylates, ethylene/alkylmethacrylates, ethylene/vinyl acetate or ethylene/acrylic acidcopolymers and their salts (ionomers) and terpolymers of ethylene withpropylene and a diene, such as hexadiene, dicyclopentadiene orethylidene-norbornene; as well as mixtures of such copolymers and theirmixtures with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/EVA, LDPE/EAA,LLDPE/EVA and LLDPE/EAA.

3a. Hydrocarbon resins (for example C₅ -C₉) and hydrogenatedmodifications thereof (for example tackyfiers).

4. Polystyrene, poly-(p-methylstyrene), poly-(α-methylstyrene).

5. Copolymers of styrene or -methylstyrene with dienes or acrylicderivatives, such as, for example, styrene/acrylonitrile, styrene/alkylmethacrylate, styrene/maleic anhydride, styrene/butadiene/ethylacrylate, styrene/acrylonitrile/methyl acrylate; mixtures of high impactstrength from styrene copolymers and another polymer, such as, forexample, from a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrene,such as, for example, styrene/butadiene/styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

6. Graft copolymers of styrene or o-methylstyrene such as, for example,styrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene and maleic anhydride ormaleimide on polybutadiene; styrene, acrylonitrile and maleic anhydrideor maleimide on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene, styrene and alkyl acrylates ormethacrylates on polybutadiene, styrene and acrylonitrile onethylene/propylene/diene terpolymers, styrene and acrylonitrile onpolyacrylates or polymethacrylates, styrene and acrylonitrile onacrylate/butadiene copolymers, as well as mixtures thereof with thecopolymers listed under 5), for instance the copolymer mixtures known asABS, MBS, ASA and AES polymers.

7. Halogen-containing polymers, such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, epichlorohydrinhomo- and copolymers, polymers from halogen-containing vinyl compounds,as for example polyvinyl chloride, polyvinylidene chloride, polyvinylfluoride, polyvinylidene fluoride, as well as copolymers thereof, as forexample vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetateor vinylidene chloride/vinyl acetate copolymers.

8. Polymers which are derived from α,β-unsaturated acids and derivativesthereof, such as polyacrylates and polymethacrylates, polyacrylamide andpolyacrylonitrile.

9. Copolymers from the monomers mentioned under 8) with each other orwith other unsaturated monomers, such as, for instance,acrylonitrile/butadiene, acrylonitrile/alkyl acrylate, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers oracrylonitrile/alkyl methacrylate/butadiene terpolymers.

10. Polymers which are derived from unsaturated alcohols and amines, oracyl derivatives thereof or acetals thereof, such as polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallylmelamine; aswell as their copolymers with olefins mentioned in 1) above.

11. Homopolymers and copolymers of cyclic ethers, such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bis-glycidyl ethers.

12. Polyacetals, such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

13. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with polystyrene or polyamides.

14. Polyurethanes which are derived from polyethers, polyesters orpolybutadienes with terminal hydroxyl groups on the one hand and on theother hand aliphatic or aromatic polyisocyanates, as well as precursorsthereof (polyisocyanates, polyols or prepolymers).

15. Polyamides and copolyamides which are derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6,6/10, 9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamidesobtained by condensation of m-xylylenediamine and adipic acid;polyamides prepared from hexamethylenediamine and isophthalic or/andterephthalic acid and optionally an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethylene-terephthalamide orpoly-m-phenylene-isophthalamide. Further, copolymers of theaforementioned polyamides with polyolefins, olefin copolymers, ionomersor chemically bonded or grafted elastomers; or with polyethers, such as,for instance, with polyethylene glycols, polypropylene glycols orpolytetramethylene glycols. Polyamides or copolyamides modified withEPDM or ABS. Polyamides condensed during processing (RIM-polyamidesystems).

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters which are derived from dicarboxylic acids and diolsand/or from hydroxycarboxylic acids or the corresponding lactones, suchas polyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate,poly-[2,2-(4-hydroxyphenyl)-propane] terephthalate andpolyhydroxybenzoates as well as block copolyether-esters derived frompolyethers having hydroxyl end groups.

18. Polycarbonates and polyester-carbonates.

19. Polysulfones, polyether-sulfones and polyether-ketones.

20. Crosslinked polymers which are derived from aldehydes on the onehand and phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins and melamineformaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins which are derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crossslinking agents, and also halogen-containingmodifications thereof of low inflammability.

23. Thermosetting acrylic resins, derived from substituted acrylicesters, such as epoxy-acrylates, urethane-acrylates orpolyesteracrylates.

24. Alkyd resins, polyester resins or acrylate resins in admixture withmelamine resins, urea resins, polyisocyanates or epoxide resins ascrosslinking agents.

25. Crosslinked epoxide resins which are derived from polyepoxides, forexample from bis-glycidyl ethers or from cycloaliphatic diepoxides.

26. Natural polymers, such as cellulose, rubber, gelatine andderivatives thereof which are chemically modified in a polymerhomologousmanner, such as cellulose acetates, cellulose propionates and cellulosebutyrates, or cellulose ethers, such as methylcellulose; rosins andtheir derivatives.

27. Mixtures of polymers as mentioned above, for example PP/EPDM,polyamide 6/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ASA, PC/PBT,PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,POM/acrylate, POM/MBS, PPE/HIPS, PPE/PA 6.6 and copolymers, PA/HDPE,PA/PP, PA/PPE.

28. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, which materials may be used as plasticizers forpolymers or as textile spinning oils, as well as aqueous emulsions ofsuch materials.

29. Aqueous emulsions of natural or synthetic rubbers, for examplenatural latices or latices of carboxylated styrene/butadiene copolymers.

The compounds of the formula (I) are particularly suitable for improvingthe light stability, heat stability and oxidation stability ofpolyolefins, especially polyethylene and polypropylene. The compounds ofthe formula (I) can be used in mixtures with organic materials invarious proportions depending on the nature of the material to bestabilized, on the end use and on the presence of other additives.

In general, it is appropriate to use, for example, 0.01 to 5 % by weightof the compounds of the formula (I) relative to the weight of thematerial to be stabilized, preferably from 0.05 to 1 %.

The compounds of the formula (I) can be incorporated in the polymericmaterials by various processes, such as e.g. dry mixing in the form ofpowder, or wet mixing in the form of solutions or suspensions or also inthe form of a masterbatch; in such operations, the polymer can be usedin the form of e.g. powder, granules, solutions, suspensions or in theform of latices.

The materials stabilized with the products of the formula (I) can beused for the production of e.g. mouldings, filmed, tapes, monofilaments,surface coatings and the like.

If desired, other conventional additives for synthetic polymers, such ase.g. antioxidants, UV absorbers, nickel stabilizers, pigments, fillers,plasticizers, antistatic agents, flameproofing agents, lubricants,corrosion inhibitors and metal deactivators, can be added to themixtures of the compounds of the formula (I) with the organic materials.

Particular examples of additives which can be used in admixture with thecompounds of the formula (I) are:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol.

1.2. Alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol.

1.3. Hydroxylated thiodiphenyl ethers, for example2,2'-thiobis(6-tertbutyl-4-methylphenol), 2,2'-thiobis(4-octylphenol),4,4'-thiobis(6-tert-butyl-3-methylphenol),4,4'-thiobis(6-tert-butyl-2-methylphenol).

1.4. Alkylidenebisphenols, for example2,2'-methylenebis(6-tert-butyl-4-methylphenol),2,2'-methylenebis(6-tert-butyl-4-ethylphenol),2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2'-methylenebis-(4-methyl-6-cyclohexylphenol),2,2'-methylenebis(6-nonyl-4-methylphenol),2,2'-methylenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(4,6-di-tert-butylphenol),2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2'-methylenebis[6-(α,α-dimethylbenzyl)- 4-nonylphenol],4,4'-methylenebis(2,6-di-tert-butylphenol),4,4'-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate,bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4methylphenyl] terephthalate.

1.5. Benzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiolterephthalate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, calcium saltof monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.6. Acylaminophenols, for example lauric acid 4-hydroxyanilide, stearicacid 4-hydroxyanilide,2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine,octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, diethylene glycol,octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol,neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethyleneglycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, diethyleneglycol, octadecanol, triethylene glycol, 1,6-hexanediol,pentaerythritol, neopentyl glycol, tris(hydroxyethyl) isocyanurate,thiodiethylene glycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.

1.9. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, diethylene glycol,octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol,neopentyl glycol, tris(hydroxyethyl) isocyanurate, thiodiethyleneglycol, N,N'-bis(hydroxyethyl)oxalic acid diamide.

1.10. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example the 5'-methyl,3',5'-di-tert-butyl, 5'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl),5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl,3'-secbutyl-5'-tert-butyl, 4'-octoxy,3',5'-di-tert-amyl and3',5'-bis(α,α-dimethylbenzyl) derivatives.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and substituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyanoβ-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, e.g.of the methyl or ethyl ester, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethylpiperidyl) sebacate,bis(1,2,2,6,6-pentmethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensationproduct of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine andsuccinic acid, the condensation product ofN,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane-tetracarboxylate,1,1'-(1,2-ethanediyl)bis-(3,3,5,5-tetramethyl-piperazinone).

2.7. Oxalic acid diamides, for example 4,4'-dioctyloxyoxanilide,2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,2,2'-didodecyloxy-5,5'-di-tertbutyloxanilide,2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixtures with2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy-disubstituted oxanilides and mixtures of o-andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1.3.5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxy-phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3.5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N'-diphenyloxalic acid diamide,N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine,N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalodihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite,tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonite,3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetra-oxa-3,9-diphosphaspiro[5.5]-undecane.

5. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

6. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

8. Nucleating agents, for example 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

9. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

10. Other additives, for example plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, antistatic agentsand blowing agents.

In order to illustrate the present invention more clearly, severalexamples of the preparation of compounds of the formula (I) aredescribed below; these examples are given by way of illustration onlyand do not imply any restriction. The compounds of Examples 2, 8, 10, 14and 17 are especially preferred compounds of formula (I).

EXAMPLE 1: Preparation of the Compound ##STR41##

A solution of 24.1 g (0.13 mol) of cyanuric chloride in 150 ml ofmesitylene is slowly added to a solution, cooled to -20° C., of 95.2 g(0.26 mol) ofN-methyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,3-propanediaminein 120 ml of mesitylene, while maintaining the temperature at -15° to-20° C.

The mixture is stirred for one hour at ambient temperature, a solutionof 10.4 g (0.26 mol) of sodium hydroxide in 30 ml of water is added andthe mixture is heated for 4 hours at 60° C. The aqueous phase isseparated off, 7.6 g (0.065 mol) of 1,6-hexanediamine and 35.9 g (0.26mol) of ground anhydrous potassium carbonate are added and the mixtureis heated for 18 hours under reflux with elimination of the water ofreaction.

After cooling to about 50° C., the reaction mixture is filtered andevaporated in vacuo (2 mbar). The resulting oily residue is taken up inaqueous acetone (10% of water), from which the product of melting point70°-74° C. crystallizes.

Analysis for C₁₀₀ H₁₉₄ N₂₄

Calculated: C=69.32%; H=11.28%; N=19.40%

Found: C=69.01%; H=11.20%; N=19.25%.

EXAMPLES 2-11

Following the procedure described in Example 1, but using theappropriate reagents, the following compounds of the formula ##STR42##are prepared.

    __________________________________________________________________________    Example                                                                            W A                         m.p. (°C.)                            __________________________________________________________________________    2    2                                                                                ##STR43##                91-94                                        3    2                                                                                ##STR44##                233-236                                      4    2                                                                                ##STR45##                82-87                                        5    2 NH(CH.sub.2).sub.3NH(CH.sub.2).sub.3NH                                                                  53-57                                        6    3                                                                                ##STR46##                90-94                                        7    3                                                                                ##STR47##                100-105                                      8    3                                                                                ##STR48##                79-83                                        9    3                                                                                ##STR49##                 96-100                                      10   3                                                                                ##STR50##                72-76                                        11   4                                                                                ##STR51##                109-113                                      __________________________________________________________________________

EXAMPLE 12: Preparation of the Compound ##STR52## 11.5 g (0.054 mol) ofN-(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamine are added to asolution, cooled to -20° C., of 10.0 g (0.054 mol) of cyanuric chloridein 100 ml of xylene, while maintaining the temperature at -15° C. to-20° C. The mixture is stirred one hour at 0° C., a solution of 2.27 g(0.057 mol) of sodium hydroxide in 10 ml of water is added and themixture is stirred for 2 hours at room temperature. 19.84 g (0.054 mol)ofN-methyl-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,3-propanediamineare added and the mixture is heated one hour at 40° C. A solution of2.27 g (0.057 mol) of sodium hydroxide is added at 35° C. and themixture is heated three hours at 60° C. After cooling to roomtemperature, the aqueous phase is separated off, 2.36 g (0.018 mol) ofbis-(3-aminopropyl)amine and 4.32 g (0.108 mol) of sodium hydroxide areadded and the mixture is heated for 10 hours under reflux withelimination of the water of reaction. After cooling, the mixture iswashed repeatedly with water and the solution evaporated in vacuo (2mbar). The product has a melting point of 87°-92° C.

Analysis for C₁₂₀ H₂₃₀ N₃₀

Calculated: C=68.85% ; H=11.07% ; N=20.07%

Found : C=68.67% ; H=10.95% ; N=19.90%.

EXAMPLE 13: Preparation of the Compound ##STR53## 10.1 g (0.004 mol) ofthe compound from Example 6 are dissolved in a solution of 9.3 g (0.202mol) of formic acid in 70 ml of water.

6.72 g (0.224 mol) of paraformaldehyde are added and the mixture isheated under reflux for 10 hours.

After cooling to ambient temperature, a solution of 16 g (0.4 mol) ofsodium hydroxide in 50 ml of water is added; the resulting precipitateis separated off by filtration, washed repeatedly with water and driedat 100° C. in vacuo (2 mbar). The product has a melting point of114°-118° C.

Analysis for C₁₅₉ H₃₀₈ N₃₆

Calculated: C=70.10%; H=11.39%; N=18.51%

Found: C=69.90%, H=11.34%; 18.52%.

Examples 14-16

Following the procedure described in Example 13, but using theappropriate reagents, the following compounds of the formula ##STR54##are prepared.

    __________________________________________________________________________    Example                                                                            W A                      m.p. (°C.)                               __________________________________________________________________________    14   3                                                                                ##STR55##              97-101                                         15   3                                                                                ##STR56##             105-109                                         16   4                                                                                ##STR57##             116-121                                         __________________________________________________________________________

EXAMPLE 17: Preparation of the Compound ##STR58## A mixture consistingof 3.4 g (0.074 mol) of formic acid and of a solution obtained bydissolving 2.56 g (0.083 mol) of paraformaldehyde in 4.6 ml of 2%aqueous NaOH solution is added in the course of about 2 hours to asolution of 14.05 g (0.005 mol) of the product described in example 7 in30 ml of xylene, heated to 110° C., the water added and the water ofreaction simultaneously being separated off azeotropically.

The mixture is then cooled to 70°-80° C. and a solution of 0.8 g ofsodium hydroxide in 10 ml of water is added. The aqueous layer isseparated off and the mixture is dehydrated, separating off the waterazeotropically. The solution is then evaporated in vacuo giving aproduct of melting point 95°-99° C.

Analysis for C₁₅₉ H₃₀₈ N₃₆

Calculated: C=70.10% ; H=11.40% ; N=18.51%

Found: C=69.62% ; H=11.25% ; N=18.32%.

EXAMPLE 18: Light-stabilizing Action in Polypropylene Tapes

1 g of each of the compounds indicated in Table 1, 0.5 g oftris-(2,4-di-t-butylphenyl) phosphite, 0.5 g of pentaerythritoltetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate] and 1 g ofcalcium stearate are mixed in a slow mixer with 1,000 g of polypropylenepowder of melt index=2 g/10 minutes (measured at 230° C. and 2.16 kg).

The mixtures are extruded at 200°-220° C. to give polymer granules whichare then converted into stretched tapes of 50 pm thickness and 2.5 mmwidth, using a pilot-type apparatus (Leonard-Sumirago (VA) Italy) andoperating under the following conditions:

extruder temperature: 210°-230° C.

head temperature: 240°-260° C.

stretch ratio: 1:6

The tapes thus prepared are exposed, mounted on a white card, in a 65 WRWeather-O-Meter (ASTM G26-77) at a black panel temperature of 63° C.

The residual tenacity is measured on samples, taken after various timesof exposure to light, by means of a constant-speed tensometer; theexposure time (in hours) needed to halve the initial tenacity is thencalculated (T₅₀).

Tapes prepared under the same conditions as indicated above, but withoutthe addition of stabilizer, are exposed for comparison.

The results obtained are shown in Table 1:

                  TABLE 1                                                         ______________________________________                                        Stabilizer          T.sub.50 (hours)                                          ______________________________________                                        without stabilizer    500                                                     compound from Example 1                                                                           3,050                                                     compound from Example 2                                                                           3,140                                                     compound from Example 4                                                                           3,190                                                     compound from Example 6                                                                           2,520                                                     compound from Example 7                                                                           2,150                                                     compound from Example 8                                                                           3,270                                                     compound from Example 9                                                                           2,600                                                     compound from Example 11                                                                          2,520                                                     compound from Example 13                                                                          3,090                                                     ______________________________________                                    

EXAMPLE 19: Light-stabilizing Action in Polypropylene Fibres

2.5 g each of the products indicated in Table 2, 0.5 g oftris-(2,4-di-t-butylphenyl phosphite, 0.5 g of calcium monoethyl3,5-di-t-butyl-4-hydroxybenzylphosphonate, 1 g of calcium stearate and2.5 g of titaniumdioxide are mixed in a slow mixer with 1,000 g ofpolypropylene powder of melt index=12 g/10 minutes (measured at 230° C.and 2.16 kg).

The mixtures are extruded at 200°-220° C. to give polymer granules whichare then converted into fibres, using a pilot-type apparatus(Leonard-Sumirago (VA) Italy) and operating under the followingconditions:

extruder temperature: 200°-230° C.

head temperature: 255°-260° C.

stretch ratio: 1:3.5

denier: 11 dtex per filament

The fibres thus prepared are exposed, mounted on a white card, in amodel 65 WR Weather-O-Meter (ASTM G 26-77) at a black panel temperatureof 63° C.

The residual tenacity is measured on samples, taken after various timesof exposure to light, by means of a constant-speed tensometer; theexposure time in hours) needed to halve the initial tenacity is thencalculated (T₅₀).

Fibres prepared under the same conditions as indicated above, butwithout the addition of compounds according to the invention, areexposed for comparison.

The results obtained are shown in Table 2:

                  TABLE 2                                                         ______________________________________                                        Stabilizer          T.sub.50 (hours)                                          ______________________________________                                        without stabilizer    150                                                     compound from Example 1                                                                           1,640                                                     compound from Example 2                                                                           1,830                                                     compound from Example 3                                                                           1,650                                                     compound from Example 5                                                                           1,640                                                     compound from Example 6                                                                           1,510                                                     compound from Example 7                                                                           1,690                                                     compound from Example 8                                                                           1,840                                                     compound from Example 9                                                                           1,510                                                     compound from Example 10                                                                          1,780                                                     compound from Example 11                                                                          1,470                                                     compound from Example 12                                                                          1,660                                                     compound from Example 13                                                                          1,500                                                     compound from Example 14                                                                          1,840                                                     compound from Example 15                                                                          1,520                                                     compound from Example 17                                                                          1,730                                                     ______________________________________                                    

What is claimed is:
 1. A compound of formula I ##STR59## in which R₁ ishydrogen, C₁ -C₈ alkyl, 0°, OH, NO, CH₂ CN, C₁ -C₁₈ alkoxy, C₅ -C₁₂cycloalkoxy, C₃ -C₆ alkenyl, C₇ -C₉ phenylalkyl which is unsubstitutedor mono, di-or tri-substituted on the phenyl by C₁ -C₄ alkyl, C₁ -C₈-acyl or C₂ -C₄ alkyl substituted in the 2-, 3- or 4-position by OH;R₂is C₂ -C₁₂ alkylene; R₃ is a group of formula II ##STR60## with R₁ andR₂ being as defined above, or R₃ is a group --OR₄, --SR₄ or ##STR61## inwhich R₄ is C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl which is unsubstituted ormono-, di- or tri-substituted by C₁ -C₄ alkyl, C₃ -C₁₈ alkenyl, phenylwhich is unsubstituted or mono, di- or tri-substituted by C₁ -C₄ alkyl,C₇ -C₉ -phenylalkyl which is unsubstituted or mono, di- ortri-substituted on the phenyl by C₁ -C₄ alkyl, or a group of the formula(III) ##STR62## where R₇ has any of the meanings given for R₁ ; R₅ andR₆ which can be identical or different are hydrogen, C₁ -C₁₈ alkyl, C₅-C₁₂ cycloalkyl which is unsubstituted or mono, di- or tri-substitutedby C₁ -C₄ alkyl, C₇ -C₉ -phenylalkyl which is unsubstituted or mono-,di- or tri-substituted on the phenyl by C₁ -C₄ alkyl, C₂ -C₄ alkylsubstituted in the 2-, 3- or 4-position by OH, by C₁ -C₈ alkoxy or bydi-(C₁ -C₄ alkyl)-amino, C₃ -C₁₈ -alkenyl, tetrahydrofurfuryl or a groupof the formula (III), or R₅ and R₆, together with the nitrogen atom towhich they are linked, form part of a 5-membered to 7-memberedheterocyclic ring which is 1 -pyrrolidyl, 1-piperidyl, 4-morpholinyl,4-methyl-1-piperazinyl, 1-hexahydroazepinyl,5,5,7-trimethyl-1-homopiperazinyl or4,5,5,7-tetramethyl-1-homopiperazinyl; and w is an integer from 2 to 6;and when w is 2, A is one of the groups of the formula (IVa)-(IVd)##STR63## in which R₈ is C₂ -C₁₂ alkylene, cyclohexylene,cyclohexylenedimethylene, methylenedicyclohexylene, (C₂ -C₆alkylidene)-dicyclohexylene, phenylene, (C₂ -C₆ alkylidene)-diphenylene,xylylene or C₄ -C₁₂ alkylene interrupted by 1, 2 or 3 oxygen atoms; R₉and R₁₁ which can be identical or different are hydrogen, C₁ -C₁₈ alkyl,C₅ -C₁₂ cycloalkyl which is unsubstituted or mono-, di- ortri-substituted by C₁ -C₄ alkyl, C₇ -C₉ phenylalkyl which isunsubstituted or mono-, di- or tri-substituted on the phenyl by C₁ -C₄-alkyl, or a group of the formula (III); R₁₀ is as defined above for R₈or C₄ -C₁₂ alkylene interrupted by 1 or 2 groups ##STR64## where R₁₅ hasany of the meanings given above for R₉ and R₁₁, or is one of the groupsof the formula (Va)-Vd) ##STR65## where R₁₆ is hydrogen, C₁ -C₁₈ alkyl,C₅ -C₁₂ cycloalkyl which is unsubstituted or mono, di- ortri-substituted by C₁ -C₄ alkyl, C₂ -C₁₈ alkenyl, phenyl which isunsubstituted or mono-, di- or tri-substituted by C₁ -C₄ -alkyl or an OHgroup or mixture thereof, C₇ -C₉ phenylalkyl which is unsubstituted ormono-, di-or tri-substituted on the phenyl by C₁ -C₄ alkyl or an OHgroup or mixture thereof; R₁₇ is C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl whichis unsubstituted or mono-, di- or tri-substitutedc by C₁ -C₄ alkyl, C₃-C₁₈ alkenyl or a group of the formula (III); R₁₈ is C₁ -C₁₈ alkyl orphenyl which is unsubstituted or mono-, di- or tri-substituted by C₁ -C₄alkyl; m is zero or 1; R₁₂ is hydrogen or methyl; n is zero, 1, 2, 3 or4; R₁₃ and R₁₄ which are identical or different are as defined above forR₉ and R₁₁ ; p and q which can be identical or different are integersfrom 2 to 6; and r is zero or 1; when w is 3, A is one of the groups ofthe formula (VIa)-(VIc) ##STR66## in which R₁₉, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆and R₂₈ which can be identical or different are as defined above for R₉and R₁₁ ; R₂₀ and R₂₁ which can be identical or different are C₂ -C₁₂alkylene or C₄ -C₁₂ alkylene interrupted by a group ##STR67## with R₂₉being defined as above for R₁₅ ; s and v which can be identical ordifferent are integers from 2 to 6; t is zero or 1; and R₂₇ is C₂ -C₁₂alkylene, and when w is 4,5 or 6, A is additionally a group of theformula (VII) ##STR68## in which R₃₀ and R₃₃ which can be identical ordifferent are as defined above for R₉ and R₁₁ ; R₃₁ and R₃₂ which can beidentical or different are C₂ -C₁₂ alkylene; and xi is 1, 2 or 3, and,when w is 4, A is also one of the groups of the formula (VIIIa)-(VIIIc)##STR69## in which R₃₄, R₃₇, R₃₈ and R₄₁ which can be identical ordifferent are as defined above for R₉ and R₁₁ ; R₃₅, R₃₆, R₃₉ and R₄₀which can be identical or different are C₂ -C₁₂ alkylene; D₁ is C₂ -C₁₂alkylene, 2-hydroxytrimethylene, --CH₂ CO--, xylylene or one of thegroups of the formula (IXa) or (IXb) ##STR70## in which R₄₃ is a directbond, C₁ -C₁₂ alkylene, cyclohexylene or phenylene; R₄₄ is as definedabove for R₈ ; and R₄₂ is as defined above for R₃ ; and when w is 6, Ais also one of the groups of the formula (Xa)-(Xc) ##STR71## in whichR₄₅, R₄₉, R₅₀ and R₅₃ which can be identical or different are as definedabove for R₉ and R₁₁ ; R₄₆, R₄₇, R₄₈, R₅₁ and R₅₂ which can be identicalor different are C₂ -C₁₂ alkylene; and D₂ is as defined above for D₁. 2.A compound of the formula (I) according to claim 1, wherein R₁ ishydrogen, C₁ -C₄ alkyl, OH, C₆ -C₁₂ alkoxy, C₅ -C₈ cycloalkoxy, allyl,benzyl, acetyl or 2-hydroxyethyl.
 3. A compound of the formula (I)according to claim 1, wherein R₂ is C₂ -C₁₀ alkylene, R₃, is a group ofthe formula (II), a group --OR₄, --SR₄ or ##STR72## in which R₄ is C₁-C₁₂ alkyl, C₅ -C₈ cycloalkyl which is unsubstitued or mono-, di- ortri-substituted by C₁ -C₄ alkyl, C₃ -C₁₂ alkenyl, phenyl, benzyl or agroup of the formula (III), R₅ and R₆ which can be identical ordifferent are hydrogen, C₁ -C₁₈ alkyl, C₅ -C₈ cycloalkyl which isunsubstituted or mono-, di- or tri-substituted by C₁ -C₄ alkyl, benzyl,C₂ -C₃ alkyl substituted in the 2- or 3-position by OH, by C₁ -C₄ alkoxyor by di-(C₁ -C₄ alkyl)-amino, allyl, oleyl, tetrahydrofurfuryl or agroup of the formula (III), or the group ##STR73## is 1-pyrrolidyl,1-piperidyl, 4-morpholinyl or 1-hexahydroazepinyl, 1 is an integer from2 to 6 and, if 1 is 2, A is one of the groups of formula (IVa)-(IVd) inwhich R₈ is C₂ -C₁₀ alkylene, cyclohexylene, cyclohexylenedimethylene,methylenedicyclohexylene, isopropylidenedicyclohexylene,isopropylidenediphenylene or C₄ -C₁₀ alkylene interrupted by 1, 2 or 3oxygen atoms, R₉ and R₁₁ which can be identical or different arehydrogen, C₁ -C₁₂ alkyl, C₅ -C₈ cycloalkyl which is unsubstituted ormono-, di- or tri-substituted by C₁ -C₄ alkyl, benzyl or a group of theformula (III), R₁₀ is as defined above for R₈ or is C₄ -C₁₂ alkyleneinterrupted by 1 or 2 group ##STR74## where R₁₅ has any of the meaningsgiven for R₉ and R₁₁, or is one of the groups of the formula (Va)-(Vd)in which R₁₆ is hydrogen, C₁ -C₁₇ alkyl, C₅ -C₈ cycloalkyl which isunsubstituted or mono-, di-or tri-substituted by C₁ -C₄ alkyl, C₂ -C₁₇alkenyl, phenyl which is unsubstituted or mono-, di- or tri-substitutedby C₁ -C₄ alkyl and/or an OH group, C₇ -C₈ phenylalkyl which isunsubstituted or mono-, di- or trisubstituted on the phenyl by C₁ -C₄alkyl and/or an OH group, R₁₇ is C₁ -C₁₈ alkyl, C₅ -C₈ cycloalkyl whichis unsubstituted or mono-, di- or tri-substituted by C₁ -C₄ alkyl, C₃-C₁₈ alkenyl or a group of the formula (III) and R₁₈ is C₁ -C₁₂ alkyl,phenyl or tolyl, m is zero or 1, R₁₂ is hydrogen or methyl, n is zero,1, 2, 3 or 4, R₁₃ and R₁₄ which can be identical or different are asdefined above for R₉ and R₁₁, p and q which can be identical ordifferent are 2 or 3 and r is zero or 1, and, if 1 is 3, A is one of thegroups of the formula (VIa)-(VIc) in which R₁₉, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆and R₂₈ which can be identical or different are as defined above for R₉and R₁₁ ; R₂₀ and R₂₁ which can be identical or different are C₂ -C₁₀alkylene or C₄ -C₁₂ alkylene which is interrupted by a group ##STR75##with R₂₉ being as defined above for R₁₅, s and v which can be i ordifferent are integers from 2 to 6, t is zero or 1 and R₂₇ is C₂ -C₁₀alkylene, and, when w is 4, 5 or 6, A is a group of the formula (VII) inwhich R₃₀ and R₃₃ which can be identical or different are as definedabove for R₉ and R₁₁ ; R₃₁ and R₃₂ which can be identical or differentare C₂ -C₁₀ alkylene; and x is 1, 2 or 3, and, when w is 4, A can alsobe one of the groups of the formula (VIIIa)-(VIIIc) in which R₃₄, R₃₇,R₃₈ and R₄₁ which can be identical or different are as defined above forR₉ and R₁₁ ; R₃₅, R₃₆, R₃₉ and R₄₀ which can be identical or differentare C₂ -C₁₀ alkylene, D₁ is C₂ -C₁₀ alkylene, 2-hydroxytrimethylene,--CH₂ CO--, xylylene or one of the groups of the formula (IXa) or (IXb)in which R₄₃ is a direct bond or C₁ -C₁₀ alkylene, R₄₄ is as definedabove for R₈ ; and R₄₂ is as defined above for R₃ and, when w is 6, A isalso one of the groups of the formula (Xa)-(Xc) in which R₄₅, R₄₉, R₅₀and R₅₃ which can be identical or different are as defined above for R₉and R₁₁ ; R₄₆, R₄₇, R₄₈, R₅₁ and R₅₂ which can be identical or differentare C₂ -C₁₀ alkylene; and D₂ is as defined above for D₁.
 4. A compoundof the formula (I) according to claim 1, wherein R₂ is C₂ -C₈ alkylene;R₃ is a group of the formula (II), a group --OR₄ or ##STR76## in whichR₄ is C₁ -C₈ alkyl, cyclohexyl which is unsubstituted or mono-, di- ortri-substituted by C₁ -C₄ alkyl, allyl, undecenyl, phenyl, benzyl or agroup of the formula (III); R₅ and R₆ which can be identical ordifferent are hydrogen, C₁ -C₁₂ alkyl, cyclohexyl which is unsubstitutedor mono-, di- or tri-substituted by C₁ -C₄ alkyl, benzyl, C₂ -C₃ alkylsubstituted in the 2- or 3-position by OH, by methoxy, by ethoxy, bydimethylamino or by diethylamino, allyl, tetrahydrofurfuryl or a groupof the formula (III), or the group ##STR77## is 4-morpholinyl; w is aninteger from 2 to 6; and, when w is 2, A is one of the groups of theformula (IVb)-(IVd) in which R₉ and R₁₁ which can be identical ordifferent are hydrogen, C₁ -C₈ alkyl, cyclohexyl which is unsubstitutedor mono-, di- or trisubstituted by C₁ -C₄ alkyl, benzyl or a group ofthe formula (III); R₁₀ is C₂ -C₈ alkylene, cyclohexylenedimethylene,methylenedicyclohexylene, C₄ -C₈ alkylene interrupted by 1 or 2 oxygenatoms or C₄ -C₁₂ alkylene interrupted by 1 or 2 groups ##STR78## whereR₁₅ has any of the meanings given for R₉ and R₁₁, or is one of thegroups of the formula (Va)-(Vc) in which R₁₆ is C₁ -C₁₇ alkyl,cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C₁-C₄ alkyl, C₂ -C₁₀ alkenyl, phenyl, 3,5-di-t-butyl-4-hydroxyphenyl,benzyl or 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl; R₁₇ is C₁ -C₁₈ alkyl,cyclohexyl which is unsubstituted or mono-, di- or tri-substituted by C₁-C₄ alkyl, allyl, undecenyl, oleyl or a group of the formula (III); m iszero or 1; R₁₂ is hydrogen or methyl; n is zero, 1, 2 or 3; R₁₃ and R₁₄which can be identical or different are as defined above for R₉ and R₁₁; p and q which can be identical or different are 2 or 3; and r is zeroor 1;, and, when w is 3, A is a group of the formula (VIa) in which R₁₉and R₂₂ which can be identical or different are as defined above for R₉and R₁₁ ; R₂₀ and R₂₁ which can be identical or different are C₂ -C₈alkylene and R₂₀ is also C₄ -C₁₂ alkylene interrupted by a group##STR79## with R₂₉ being as defined above for R₁₅ ; and, when w is 4, 5or 6, A is a group of the formula (VII) in which R₃₀ and R₃₃ which canbe identical or different are as defined above for R₉ and R₁₁ ; R₃₁ andR₃₂ which can be identical or different are C₂ -C₈ alkylene and x is 1,2 or 3; and, when w is 4, A is also a group of the formula (VIIIa) inwhich R₃₄ and R₃₇ which can be identical or different are as definedabove for R₉ and R₁₁ ; R₃₅ and R₃₆ which can be identical or differentare C₂ -C₈ alkylene and D₁ is C₂ -C₈ alkylene, 2-hydroxytrimethylene,xylylene or a group of the formula (IXa) or (IXb) in which R₄₃ is adirect bond or C₁ -C₈ alkylene; and R₄₄ is C₄ - C₈ alkylene,3-oxapentane-1,5-diyl, cyclohexylenedimethylene orisopropylidenedicyclohexylene; and, when w is 6, A is also a group ofthe formula (Xa) in which R₄₅ and R₄₉ which can be identical ordifferent are as defined above for R₉ and R₁₁ ; R₄₆, R₄₇ and R₄₈ whichcan be identical or different are C₂ -C₈ alkylene and D₂ is as definedabove for D₁.
 5. A compound of the formula (I) according to claim 1,wherein R₂ is C₂ -C₆ alkylene; R₃ is a group of the formula (II) or agroup ##STR80## in which R₅ and R₆ which can be identical or differentare C₁ -C₈ alkyl, cyclohexyl, benzyl, C₂ -C₃ which is substituted in the2- or 3-position by methoxy, by ethoxy, by dimethylamino ordiethylamino, allyl tetrahydrofurfuryl, 2,2,6,6-tetramethyl-4-piperidylor 1,2,2,6,6-pentamethyl-4-piperidyl, or R₅ is also hydrogen, or thegroup ##STR81## is 4-morpholinyl; and w is 2, 3 or 4, and, when w is 2,A is one of the groups of the formula (IVb)-(IVd) in which R₉ and R₁₁which can be identical or different are hydrogen, C₁ -C₄ alkyl,cyclohexyl, 2,2,6,6-tetramethyl-4-piperidyl or1,2,2,6,6-pentamethyl-4-piperidyl; R₁₀ is C₂ -C₆ alkylene,cyclohexylenedimethylene, methylenedicyclohexylene or C₄ -C₁₂ alkyleneinterrupted by 1 or 2 groups ##STR82## where R₁₅ is hydrogen, methyl ora group of the formula (Va) or (Vb) in which R₁₆ is C₁ -C₁₇ alkyl,cyclohexyl, phenyl or 2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl; and R₁₇is C₂ -C₁₈ alkyl, cyclohexyl, t-butylcyclohexyl or1,2,2,6,6-pentamethyl-4-piperidyl; and m and n are zero; R₁₃ and R₁₄which can be identical or different are as defined above for R₉ and R₁₁,p and q are 2 or 3 and r is zero or 1, and, when w is 3, A is a group ofthe formula (VIa) in which R₁₉ and R₂₂ which can be identical ordifferent are as defined above for R₉ and R₁₁ ; R₂₀ and R₂₁ which can beidentical or different are C₂ -C₆ -alkylene and R₂₀ is also C₄ -C₆alkylene interrupted by a group N-R₂₉ with R₂₉ being as defined abovefor R₁₅ ; and, when w is 4, A is a group of the formla (VII) in whichR₃₀ and R₃₃ which can be identical or different are as defined above forR₉ and R₁₁ ; R₃₁ and R₃₂ which can be identical or different are C₂ -C₆alkylene; and x is 1, or A is a group of the formula (VIIIa) in whichR₃₄ and R₃₇ which can be identical or different are as defined above forR₉ and R.sub. 11 ; R₃₅ and R₃₆ which can be identical or different areC₂ -C₆ alkylene; and D₁ is a group of the formula (IXa) or (IXb) inwhich R₄₃ is C₂ -C₈ alkylene; and R₄₄ is C₄ -C₆ alkylene,3-oxa-pentane-1,5-diyl, cyclohexylenedimethylene orisopropylidenedicyclohexylene.
 6. A compound of the formula (I)according to claim 1, wherein R₁ is hydrogen or methyl; R₂ is --(CH₂)₂₋₆--; R₃ is a group of the formula (II) with R₁ and R₂ being as definedabove; w is 2, 3 or 4 and, when w is 2, A is one of the groups of theformula (IVb)-(IVd) in which R₉ and R₁₁ which can be identical ordifferent are hydrogen, methyl, 2,2,6,6-tetramethyl-4-piperidyl or1,2,2,6,6-pentamethyl-4-piperidyl; R₁₀ is C₂ -C₆ -alkylene,methylenedicyclohexylene, C₄ -C₁₂ alkylene interrupted by 1 or 2 group##STR83## where R₁₅ is hydrogen, methyl or a group of the formula (Va)or (Vb) in which R₁₆ is C₄ -C₁₇ alkyl and R₁₇ is C₂ -C₁₈ alkyl ort-butylcyclohexyl; m and n are zero; R₁₃ and R₁₄ which can be identicalor different are as defined above for R₉ and R₁₁ ; p and q are 2 or 3;and r is zero or 1; and, when w is 3, A is a group of the formula (VIa)in which R₁₉ and R₂₂ which can be identical or different are as definedabove for R₉ and R₁₁ ; R₂₀ and R₂₁ which can be identical or differentare C₂ -C₆ -alkylene and R₂₀ is also C₄ -C₆ alkylene interrupted by agroup ##STR84## with R₂₉ being as defined above for R₁₅ ; and, when w is4, A is a group of the formula (VII) in which R₃₀ and R₃₃ which can beidentical or different are hydrogen or methyl; R₃₁ and R₃₂ which can beidentical or different are C₂ -C₃ alkylene and x is
 1. 7. A compound ofthe formula (I) according to claim 1, wherein R₁ is hydrogen or methyl;R₂ is C₂ -C₆ alkylene; R₃ is a group of the formula (II) with R₁ and R₂being as defined above; and w is 2, 3 or 4, and, when w is 2, A ispiperazine-1,4-diyl or a group of the formula (IVb) in which R₉ and R₁₁which can be identical or different are hydrogen, methyl,2,2,6,6-tetramethyl-4-piperidyl or 1,2,2,6,6-pentamethyl-4-piperidyl;R₁₀ is C₂ -C₆ alkylene, methylenedicyclohexylene or C₄ -C₁₂ alkyleneinterrupted by 1 or 2 groups ##STR85## where R₁₅ is hydrogen, methyl or(C₂ -C₄ alkoxy)carbonyl; and when w is 3, A is a group of the formula(VIa) in which R₁₉ and R₂₂ which can be identical or different arehydrogen or methyl; R₂₀ is C₂ -C₆ alkylene or C₄ -C₆ alkyleneinterrupted by a group ##STR86## with R₂₉ being as defined above for R₁₅; and R₂₁ is C₂ -C₆ alkylene; and, when w is 4, A is a group of theformula (VII) where R₃₀ and R₃₃ which can be identical or different arehydrogen or methyl; R₃₁ and R₃₂ independently of one another are C₂ -C₃alkylene; and x is
 1. 8. A compound of the formula ##STR87## wherein 1'is 2 or 3 and when 1' is 2, A' is a group ##STR88## and when 1' is 3, A'is a group ##STR89## and a compound of the formula ##STR90## wherein A"is a group ##STR91## according to claim 1.